THE ELECTROLYSIS OF SPECIFIC

ELECTROLYTES

Lij wynter
CHEMISTRY 504
 What is Electrolysis?

The chemical decomposition produced by

Passing an electric current through
A liquid or solution containing ions.

What is an electrolyte?

An electrolyte is a liquid or gel which contains ions and can

be decomposed by electrolysis.
Examples are:
Sodium hydroxide NaOH .Sodium chloride - NaCl
Nitric acid HNO3
Chloric acid HClO3
Calcium chloride - CaCl
Potassium nitrate KNO
Sulfuric acid H2SO4
 Sodium acetate C2H3NaO2
Magnesium hydroxide MgOH2 .Hydrochloric acid HCl

Cathode Reaction:
2 H (+) + 2e (-) ==> H2

4 H (+) + 4e (-) ==> 2H2

The negative cathode electrode reaction is a reduction (electron gain).

The hydrogen ions (H+) are attracted to the negative cathode and are
discharged as hydrogen gas.

The hydrogen ion or water molecules are reduced to hydrogen gas

molecules by electron gain at the negative electrode.

Anode Reaction:
2 H2O ==> O2 + 4 H (+) + 4 e (-)

But the sulfate ion is too stable and nothing happens. Instead either
hydroxide ions or water molecules are discharged and oxidized to form
oxygen.
 The hydroxide ions or water molecules are oxidized to oxygen gas
molecules by electron loss at the positive electrode

Overall equation for the electrolysis of water: 2H2O (l) ==> 2H2 (g) + O2
(g)

Concentrated Aqueous Sodium Chloride (NaCl) using inert electrodes

(platinum):

Cathode Reaction:
The negative () cathode attracts the Na+ (from sodium chloride)
and H+ ions (from water). Only the hydrogen ions are discharged at the
cathode. The more reactive a metal, the less readily its ion is reduced on the
electrode surface.

The hydrogen ions are reduced by electron (e) gain to form hydrogen
molecules at the negative electrode which attracts positive ions.

2H+(aq) + 2e ==> H2(g)

Positive ion reduction by electron gain

Anode Reaction: The positive anode attracts the negative hydroxide

OH ions (from water) and chloride Cl ions (from sodium chloride)

Only the chloride ion is discharged in appreciable quantities i.e. it is

preferentially oxidized to chlorine.
The chloride ions are oxidized by electron loss to give chlorine molecules at
the positive electrode which attracts negative ions.

An oxidation electrode reaction

2Cl(aq) 2e ==> Cl2(g)

Or 2Cl ==> Cl2 (g) + 2e

Overall equation for the electrolysis of brine: 2NaCl (aq) + 2H2O (l) ==>
H2 (g) + Cl2 (g) + 2NaOH (aq)

Products:

Hydrogen, Chlorine and Sodium Hydroxide.

Dilute Aqueous Sodium Chloride (NaCl) using inert electrodes

(platinum):

In very dilute sodium chloride solution, oxidation of hydroxide ions or

water molecules can produce oxygen gas as well as chlorine gas. At low
concentrations of chloride ion a competing oxidation of water or hydroxide
ion can occur, particularly as the concentration of hydroxide ion is
increasing as the electrolysis proceeds.

Copper (II) Sulphate -using inert electrodes (Carbon electrodes):

Cathode reaction with graphite electrodes:

The negative cathode electrode attracts Cu2+ ions (from copper sulfate) and
H+ ions (from water). Only the copper ion is discharged, being reduced to
copper metal. The less reactive a metal, the more readily its ion is reduced
on the electrode surface.

A copper deposit forms as the positive copper ions are attracted to the
negative electrode (cathode)

Cu2+ (aq) + 2e ==> Cu(s)

Positive ion reduction by electron gain

The traces of hydrogen ions are not discharged, so you not see any gas
collected above the negative electrode.

The blue colour of the copper ion will fade as the copper ions are converted
to the copper deposit on the cathode

Anode Reaction with graphite electrodes:

Oxygen gas is formed at the positive electrode, an oxidation reaction

(electron loss).

The negative sulphate ions (SO42-) or the traces of hydroxide ions (OH) are
attracted to the positive electrode. 6

But the sulfate ion is too stable and nothing happens. Instead either
hydroxide ions or water molecules are discharged and oxidized to form
oxygen.

(i) 4OH(aq) 4e ==> 2H2O (l) + O2 (g)

Negative ion oxidation by electron loss

Or 4OH(aq) ==> 2H2O (l) + O2 (g) + 4e

At the cathode, the copper ions in solution gain electrons, becoming copper atoms
and plating the cathode.
Cu2+ (aq) + 2e Cu(s)
The cathode gets thicker and thicker as the electrolysis goes on.
At the anode, copper atoms enter the solution as copper ions and the impure copper
anode loses mass.
Cu(s) 2e Cu2+ (aq)
As a copper ion is removed from solution at the cathode, a copper ion enters the
solution from the anode.
As copper is transferred from the anode to the cathode, any soluble impurities in
the copper anode dissolve in the copper (II) sulfate and are removed later.
 Pb2+ + 2e- Pb (lead metal at the (-) cathode).
2Br- - 2e- Br2 (bromine gas at the (+) anode).

Lead ions gain electrons (reduction) to form lead atoms.

Bromide ions lose electrons (oxidation) to form bromine atoms.
The bromine atoms combine to form molecules of bromine gas.

The overall reaction is:

PbBr2 (l) Pb(s) + Br2 (g)

 Aluminum oxide (Al2O3) is an ionic compound.
When it is melted the Al3+ and O2- ions are free to move
and conduct electricity. Electrolysis of the alumina/cryolite solution
gives aluminum at the cathode and oxygen at the anode.

4Al3+ + 12e- 4Al (aluminum metal at the (-) cathode) reduction.

6O2- - 12e- 3O2 (oxygen gas at the (+) anode) oxidation.

Aluminum is denser than the alumina/cryolite solution

and so it falls to the bottom of the cell
where it can be tapped off as pure liquid metal.

The overall reaction is

Aluminum oxide aluminum + oxygen.

2Al2O3 (l) 4Al (l) + 3O2 (g)
Bibliography
The sources of this information are found on the following sites.

www.gcsescience.com
www.ibchem.com
www.docbrown.info/page01/ExIndChem/electroChemistry03.htm.
com
www.ucc.ie/academic/chem/dolchem.com